Steroidal compounds and methods for obtaining the same



Patented Oct. 8, 1946 STERGIDAL COMPOUNDS AND METHODS Y FOR OBTAINING THE RomeoB. Wagner, State College, 'Pa., assignor to Parke, Davis & Compan poration of Michigan y, Detroit, Mich:, acor- No Drawing. Application May 15, 1344,

Serial No. 535,753

The invention relates to the preparation of new foseudo-sapogenin compounds from steroidal sacogenin compounds such as the lilagenin type and the yuccagenin type described in my copending application, Serial No. 535,748, filed May 15, 944. The new pseudo compounds are useful as intermediates for preparations of physiologically active compounds, such as sex hormones.

The reaction by Which steroidal sapogenins are isomerized to the pseudo-genius have been described in detail in the copending Patents Nos. 2,352,848 and 2,352,852, issued July 4, 1944. These also include proof of structure of the pseudogenin side chain.

The present invention relates more particularly to the preparation of pseudo-sapogenin compounds by way of isomerization of the corresponding sapogenin. The new compounds have the formula,

Where Y and Y are members of the class and groups hydrolyzable to The invention is illustrated by the following examples.

Example 1 A mixture of 10 grams of yuccagenin diacetate and 15 cc. of acetic anhydride contained in a sealed tube is heated at 200 C. for 10 hours.

5 Claims. .(Cl. 260239.5) V

at about 200 C. for 12 hours. The acetic anhydricle is removed by distillation and the residue taken up in methanol and the resulting solution treated with decolorizing charcoal and then crystallized from the methanol by concentration and cooling. The crystals are filtered oif and dried to give a product of M. P. 146 C. which also melts at 146 C. when mixed with pseudo-yuccagenin triacetate from Example 1. It gives the correct analysis for C33H4s07 and can be hydrolyzed like the triacetate of Example 1 to give pseudo-yuccagenin of M. 'P 182 C.

After removal of the acetic anhydride and treatmerit of a methanol solution of the residue with charcoal (Norite brand), the product is then crystallized from methanol to give a product of M. P. lei-145 C. Recrystallization from methanol raises the melting point to 145147 C. This is pseudo-yuccagenin triacetate.

Anal; Calcd for (3331314807! C, 71.2; H, 8.7%. Found: C, 71.5; H, 9.0%.

The triacetate can be hydrolyzed with dilute alkali, extracted with ether and crystallized from other to give needles of pseudo-yuccagem'n of M, P. i8l-i82 C.

Soc. 62, 2620 (1940)) melting at 156 C. and 30 cc. of acetic anhydride are heated in a sealed tube The transformations of these examples can be represented as follows:

OHa C 2C z 3 a I r A CH-C CHI-CH3 H W/ H L/V Yuccagenin diacetate on on E 3 3 oH-o (DH-CH H CH H 2- 2 a sum anhydride AcO- N H (e. g. A090) fll l A O C Lilagenin diacetate A020 at about 200 0.

CH3 C CHzCHz CH3 CH3 I C=O CHCHa OHnOAc I H 0 A00- Pseudo-yuccagenin triacylate (e. g. triacetate) Alkaline l hydrolysis CH CHJOHZ CH CHa C=O (EH-CH3 OHzOH I H O l/\/\l/\/ H Pseudo-yuccagenin Whilefor ease of. manipulation and economy and organic carboxylic acid ester groups hythe preferred isomerizing agent is acetic anhydrolyzable to dride, other lower aliphatic acid anhydrides may H also be used. The preferred temperature range lies between 190 and 200 C. although the reaca H tion also takes place as low as 170 or as high as 230. The example is intended as illustrative and 3. Compounds having the formula, the invention is not necessarily limited to the conditions and reactants therein cited. H

What I claim is: l0 O=O-OHA JH| 1. Compounds having the formula, H (BEECH:

CH: CH; CH; 1 O CH=Y c =C-CHICH! m-0H; CH=Y F--0 1 where Y and Y are lower fatty acid ester groups. Y 4. Pseudocca enin tr'ace ate ha n h My formula, W g l t W g t e Where Y and Y are members of the class OH:

OH E (|J-C CH CH 11 A (311 CH and groups hydrolyzable to l 2 oHloilc if AcO 5 A00 l 2. Compounds having the formula, V V

CH: '5. Pseudo-yuccagenin having the formula, CH; OH: I

A ore-omen, CH, I; I E e=o oH-cm OHSY OH OH H Y, I EGAN :H

l t where Y and Y are members of the class ROMEO B. WAGNER. 

